US20130026486A1 - Epitaxial substrate and method for manufacturing epitaxial substrate - Google Patents

Epitaxial substrate and method for manufacturing epitaxial substrate Download PDF

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US20130026486A1
US20130026486A1 US13/633,375 US201213633375A US2013026486A1 US 20130026486 A1 US20130026486 A1 US 20130026486A1 US 201213633375 A US201213633375 A US 201213633375A US 2013026486 A1 US2013026486 A1 US 2013026486A1
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layer
composition
base
substrate
base layer
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Makoto Miyoshi
Shigeaki Sumiya
Mikiya Ichimura
Sota Maehara
Mitsuhiro Tanaka
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NGK Insulators Ltd
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Assigned to NGK INSULATORS, LTD. reassignment NGK INSULATORS, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MIYOSHI, MAKOTO, TANAKA, MITSUHIRO, ICHIMURA, MIKIYA, MAEHARA, SOTA, SUMIYA, SHIGEAKI
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Definitions

  • the present invention relates to an epitaxial substrate for use in a semiconductor device, and particularly to an epitaxial substrate made of a group-III nitride.
  • a nitride semiconductor is attracting attention as a semiconductor material for a light-emitting device such as a LED or a LD and for a high-frequency/high-power electronic device such as a HEMT, because the nitride semiconductor has a wide band gap of direct transition type and the breakdown electric field and the saturation electron velocity thereof are high.
  • a HEMT (high electron mobility transistor) device in which a barrier layer made of AlGaN and a channel layer made of GaN are laminated takes advantage of the feature that causes a high-concentration two-dimensional electron gas (2DEG) to occur in a lamination interface (hetero interface) due to the large polarization effect (a spontaneous polarization effect and a piezo polarization effect) specific to a nitride material (for example, see Non-Patent Document 1).
  • 2DEG high-concentration two-dimensional electron gas
  • a single crystal (a different kind single crystal) having a composition different from that of a group-III nitride, such as SiC is used as a base substrate for use in a HEMT-device epitaxial substrate.
  • a buffer layer such as a strained-superlattice layer or a low-temperature growth buffer layer is generally formed as an initially-grown layer on the base substrate. Accordingly, a configuration in which a barrier layer, a channel layer, and a buffer layer are epitaxially formed on a base substrate is the most basic configuration of the HEMT-device substrate including a base substrate made of a different kind single crystal.
  • a spacer layer having a thickness of about 1 nm may be sometimes provided between the barrier layer and the channel layer, for the purpose of facilitating a spatial confinement of the two-dimensional electron gas.
  • the spacer layer is made of, for example, AlN.
  • a cap layer made of, for example, an n-type GaN layer or a superlattice layer may be sometimes formed on the barrier layer, for the purpose of controlling the energy level at the most superficial surface of the HEMT-device substrate and improving contact characteristics of contact with an electrode.
  • the HEMT device and the HEMT-device substrate involve various problems including problems concerning improvement of the performance such as increasing the power density and efficiency, problems concerning improvement of the functionality such as a normally-off operation, fundamental problems concerning a high reliability and cost reduction, and the like. Active efforts are made on each of the problems.
  • Non-Patent Document 2 it is already known that, in order that the HEMT-device epitaxial substrate can be structured with a high breakdown voltage, it is effective to increase the total film thickness of the channel layer and the barrier layer and to improve the electrical breakdown strength of both of the layers (for example, see Non-Patent Document 2).
  • a method for manufacturing a semiconductor device is also known in which an interposed layer made of AlN is formed on a Si base substrate, then a first semiconductor layer made of GaN and a second semiconductor layer made of AlN are alternately formed so as to cause convex warping as a whole, and then these layers are made contract at a subsequent temperature drop, to result in cancellation of the warping of the entire substrate (for example, see Patent Document 4).
  • the values of the lattice constants of silicon and nitride materials are greatly different from each other. This causes a misfit dislocation at an interface between the silicon substrate and a growth film, and facilitates a three-dimensional growth mode at a timing from the nucleus formation to the growth. In other words, this is a factor that hinders the formation of a good nitride epitaxial film having a low dislocation density and a flat surface.
  • the nitride material has a higher thermal expansion coefficient value than that of silicon. Therefore, in the step of lowering the temperature to the vicinity of the room temperature after a nitride film is epitaxially grown on the silicon substrate at a high temperature, a tensile stress acts in the nitride film. As a result, it is likely that cracking occurs in a film surface and large warping occurs in the substrate.
  • TMG trimethylgallium
  • the present invention has been made in view of the problems described above, and an object of the present invention is to provide a crack-free epitaxial substrate having excellent breakdown voltage properties in which a silicon substrate is used as a base substrate.
  • a first aspect of the present invention is an epitaxial substrate in which a group of group-III nitride layers are formed on a base substrate made of (111)-oriented single crystal silicon such that a (0001) crystal plane of the group of group-III nitride layers is substantially in parallel with a substrate surface of the base substrate.
  • the epitaxial substrate includes: a buffer layer including a composition modulation layer that is formed of a first composition layer made of AlN and a second composition layer made of a group-III nitride having a composition of Al x Ga 1-x N (0 ⁇ x ⁇ 1) being alternately laminated; and a crystal layer formed on the buffer layer.
  • the composition modulation layer is formed so as to satisfy the relationship of x(1) ⁇ x(2) ⁇ . . . ⁇ x(n ⁇ 1) ⁇ x(n) and x(1)>x(n), where n represents the number of laminations of each of the first composition layer and the second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of the second composition layers as counted from the base substrate side, to thereby cause a compressive strain to exist in the composition modulation layer such that the compressive strain increases in a portion more distant from the base substrate.
  • each of the second composition layers is formed so as to be in a coherent state relative to the first composition layer.
  • the epitaxial substrate according to the first aspect further includes: a first base layer made of AlN and formed on the base substrate; and a second base layer made of Al p Ga 1-p N (0 ⁇ p ⁇ 1) and formed on the first base layer.
  • the first base layer is a layer with many crystal defects configured of at least one kind from a columnar or granular crystal or domain.
  • An interface between the first base layer and the second base layer defines a three-dimensional concavo-convex surface.
  • the buffer layer is formed immediately on the second base layer.
  • a fourth aspect of the present invention is a method for manufacturing an epitaxial substrate for use in a semiconductor device, the epitaxial substrate having a group of group-III nitride layers formed on a base substrate made of (111)-oriented single crystal silicon such that a (0001) crystal plane of the group of group-III nitride layers is substantially in parallel with a substrate surface of the base substrate.
  • the method includes: a buffer layer formation step for forming a buffer layer; and a crystal layer formation step for forming a crystal layer above the buffer layer, the crystal layer being made of a group-III nitride.
  • the buffer layer formation step includes a composition modulation layer formation step for forming a composition modulation layer by alternately laminating a first composition layer made of AlN and a second composition layer made of a group-III nitride having a composition of Al x Ga 1-x N (0 ⁇ x ⁇ 1).
  • the composition modulation layer is formed in such a manner that: the relationship of x(1) ⁇ x(2) ⁇ . . .
  • n represents the number of laminations of each of the first composition layer and the second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of the second composition layers as counted from the base substrate side; and each of the second composition layers is in a coherent state relative to the first composition layer.
  • the method for manufacturing the epitaxial substrate according to the fourth aspect further includes: a first base layer formation step for forming a first base layer on the base substrate, the first base layer being made of AlN; and a second base layer formation step for forming a second base layer on the first base layer, the second base layer being made of AlGa 1-p N (0 ⁇ p ⁇ 1).
  • the first base layer formation step the first base layer is formed as a layer with many crystal defects configured of at least one kind from a columnar or granular crystal or domain, such that a surface thereof is a three-dimensional concavo-convex surface.
  • the composition modulation layer formation step the composition modulation layer is formed immediately on the second base layer.
  • the compressive strain exists in the buffer layer. Accordingly, a tensile stress caused by a difference in a thermal expansion coefficient between silicon and a group-III nitride is cancelled by the compressive strain. Therefore, a crack-free epitaxial substrate having a small amount of warping and an excellent crystal quality and excellent breakdown voltage properties can be obtained even when a silicon substrate is used as the base substrate.
  • the buffer layer is provided on the base layer having a low dislocation and an excellent surface flatness. Accordingly, the buffer layer, the crystal layer, and the like, have good crystal quality. On the other hand, an accumulation of strain energy in the second base layer is suppressed. Therefore, the effect of canceling the tensile stress exerted by the compressive strain existing in the buffer layer is not hindered by any accumulation of strain energy in the base layer.
  • FIG. 1 is a schematic cross-sectional view showing an outline configuration of an epitaxial substrate 10 according to an embodiment of the present invention.
  • FIGS. 2A , 2 B and 2 C are model diagrams showing a crystal lattice at a time when a second composition layer 32 is formed on a first composition layer 31 in a composition modulation layer 3 .
  • FIG. 3 is a diagram illustrating how the Al mole fraction was changed in main specimens of examples.
  • FIG. 1 is a schematic cross-sectional view showing an outline configuration of an epitaxial substrate 10 according to an embodiment of the present invention.
  • the epitaxial substrate 10 mainly includes a base substrate 1 , a base layer 2 , a buffer layer 5 , and a function layer 6 .
  • the buffer layer 5 includes a composition modulation layer 3 and a termination layer 4 .
  • the layers formed on the base substrate 1 will be sometimes collectively referred to as an epitaxial film.
  • the proportion of existence of Al in the group-III elements will be sometimes referred to as Al mole fraction.
  • the base substrate 1 is a wafer of (111) plane single crystal silicon having the p-type conductivity.
  • the thickness of the base substrate 1 is not particularly limited, but for convenience of handling, it is preferable to use the base substrate 1 having a thickness of several hundred ⁇ m to several mm.
  • Each of the base layer 2 , the composition modulation layer 3 , the termination layer 4 , and the function layer 6 is a layer formed of a wurtzite-type group-III nitride by using an epitaxial growth method such that a its (0001) crystal plane can be substantially in parallel with a substrate surface of the base substrate 1 .
  • these layers are formed by a metalorganic chemical vapor deposition method (MOCVD method).
  • the base layer 2 is a layer provided for the purpose of enabling each of the above-mentioned layers to be formed thereon with a good crystal quality.
  • the base layer 2 is formed in such a manner that its dislocation density is suitably reduced and it has a good crystal quality at least near its surface (near an interface with the composition modulation layer 3 ). As a result, a good crystal quality is obtained in the composition modulation layer 3 , and additionally in the layers formed thereon.
  • the base layer 2 is composed of a first base layer 2 a and a second base layer 2 b , as described below.
  • the first base layer 2 a is a layer made of AlN.
  • the first base layer 2 a is a layer configured of a large number of small columnar crystals or the like (at least one kind from columnar crystals, granular crystals, columnar domains, and granular domains) that have been grown in a direction (film formation direction) substantially perpendicular to the substrate surface of the base substrate 1 .
  • the first base layer 2 a is a layer with many defects having inferior crystal properties, in which, although uniaxial orientation is achieved along a lamination direction of the epitaxial substrate 10 , many crystal grain boundaries or dislocations exist along the lamination direction.
  • the crystal grain boundary is sometimes used as the term inclusive of domain grain boundaries and dislocations, too.
  • the interval of the crystal grain boundaries is at most about several tens nm.
  • the first base layer 2 a having this configuration is formed such that the half width of a (0002) X-ray rocking curve can be 0.5 degrees or more and 1.1 degrees or less and such that the half width of a (10-10) X-ray rocking curve can be 0.8 degrees or more and 1.1 degrees or less.
  • the half width of the (0002) X-ray rocking curve serves as an index of the magnitude of mosaicity of a c-axis tilt component or the frequency of screw dislocations.
  • the half width of the (10-10) X-ray rocking curve serves as an index of the magnitude of mosaicity of a crystal rotation component whose rotation axis is c-axis or the frequency of edge dislocations.
  • the second base layer 2 b is a layer formed on the first base layer 2 a and made of a group-III nitride having a composition of Al p Ga 1-p N (0 ⁇ p ⁇ 1).
  • An interface I 1 (a surface of the first base layer 2 a ) between the first base layer 2 a and the second base layer 2 b is a three-dimensional concavo-convex surface that reflects the outer shapes of the columnar crystals and the like included in the first base layer 2 a .
  • the fact that the interface I 1 has such a shape is clearly confirmed in, for example, a HAADF (high-angle annular dark-field) image of the epitaxial substrate 10 .
  • the HAADF image is obtained by a scanning transmission electron microscope (STEM), and is a mapping image of the integrated intensity of electron that is inelastically scattered at a high angle.
  • the image intensity is proportional to the square of an atomic number, and a portion where an atom having a greater atomic number exists is observed more brightly (more white). Therefore, the second base layer 2 b containing Ga is observed relatively bright, and the first base layer 2 a not containing Ga is observed relatively dark. Thereby, the fact that the interface I 1 therebetween is configured as a three-dimensional concavo-convex surface is easily recognized.
  • convex portions 2 c of the first base layer 2 a are located at substantially regular intervals. This is merely for convenience of illustration. Actually, the convex portions 2 c are not necessarily located at regular intervals.
  • the first base layer 2 a is formed such that the density of the convex portions 2 c can be 5 ⁇ 10 9 /cm 2 or more and 5 ⁇ 10 10 /cm 2 or less and the average interval of the convex portions 2 c can be 45 nm or more and 140 nm or less. When these ranges are satisfied, the function layer 6 having, particularly, an excellent crystal quality can be formed.
  • the convex portion 2 c of the first base layer 2 a always denotes a position substantially at the apex of an upward convex portion of the surface (interface I 1 ). From the results of experiments and observations made by the inventors of the present invention, it has been confirmed that a side wall of the convex portion 2 c is formed by a (10-11) plane or (10-12) plane of AlN.
  • the convex portions 2 c that satisfy the above-mentioned density and average interval can be formed on the surface of the first base layer 2 a .
  • the average film thickness is less than 40 nm, it is difficult to achieve a state where the substrate surface is thoroughly covered with AlN while forming the convex portions 2 c as described above.
  • the average film thickness exceeds 200 nm, flattening of an AlN surface starts to progress, to make it difficult to form the convex portions 2 c described above.
  • the formation of the first base layer 2 a is performed under predetermined epitaxial growth conditions.
  • forming the first base layer 2 a with AlN is preferable in terms of not containing Ga which forms a liquid-phase compound with silicon and in terms of easily configuring the interface I 1 as a three-dimensional concavo-convex surface because a horizontal growth is relatively unlikely to progress.
  • the first base layer 2 a that is a layer with many defects in which the crystal grain boundaries exist is interposed between the base substrate 1 and the second base layer 2 b in the above-described manner. This relieves a lattice misfit between the base substrate 1 and the second base layer 2 b , and thus an accumulation of strain energy caused by this lattice misfit is suppressed.
  • the above-described ranges of the half widths of the (0002) and (10-10) X-ray rocking curves with respect to the first base layer 2 a are set as ranges that can suitably suppress the accumulation of strain energy due to the crystal grain boundaries.
  • the interposition of the first base layer 2 a causes an enormous number of dislocations originating from the crystal grain boundaries such as the columnar crystals of the first base layer 2 a to propagate in the second base layer 2 b .
  • the interface I 1 between the first base layer 2 a and the second base layer 2 b is configured as a three-dimensional concavo-convex surface, and thereby such dislocations are effectively reduced.
  • the interface I 1 between the first base layer 2 a and the second base layer 2 b is configured as a three-dimensional concavo-convex surface, most of the dislocations caused in the first base layer 2 a are bent at the interface I 1 during the propagation (penetration) from the first base layer 2 a to the second base layer 2 b , and coalesce and disappear within the second base layer 2 b . As a result, only a small part of the dislocations originating from the first base layer 2 a penetrates through the second base layer 2 b.
  • the second base layer 2 b is formed along the shape of the surface of the first base layer 2 a (the shape of the interface I 1 ) in an initial stage of the growth, the surface thereof is gradually flattened along with the progress of the growth, and finally obtains a surface roughness of 10 nm or less.
  • the surface roughness is expressed as an average roughness ra in a region of 5 ⁇ m ⁇ 5 ⁇ m which has been measured by an AFM (atomic force microscope).
  • the second base layer 2 b is formed of a group-III nitride having a composition that contains at least Ga, which allows a horizontal growth to progress relatively easily.
  • the second base layer 2 b has an average thickness of 40 nm or more. This is because, when the average thickness is less than 40 nm, such problems arise that concaves and convexes caused by the first base layer 2 a cannot sufficiently be flattened, and that the disappearance of dislocations having propagated to the second base layer 2 b and coalesced with each other does not sufficiently occur. In a case where the average thickness is 40 nm or more, the reduction of the dislocation density and the flattening of the surface are effectively achieved. Therefore, in a technical sense, no particular limitation is put on an upper limit of the thickness of the second base layer 2 b , but from the viewpoint of the productivity, it is preferable that the thickness is about several ⁇ m or less.
  • the surface of the second base layer 2 b has a low dislocation and an excellent flatness, and therefore the layers formed thereon have a good crystal quality.
  • the composition modulation layer 3 is a part formed by a first composition layer 31 made of AlN and a second composition layer 32 made of a group-III nitride having a composition of Al x Ga 1-x N (0 ⁇ x ⁇ 1) being alternately laminated.
  • the i-th first composition layer 31 as counted from the base substrate 1 side is expressed as “31 ⁇ i>”
  • the i-th second composition layer 32 as counted from the base substrate 1 side is expressed as “32 ⁇ i>”.
  • the second composition layer 32 is formed so as to satisfy the following expressions 1 and 2, where n (n is a natural number equal to or greater than two) represents the number of the first composition layers 31 and the number of the second composition layers 32 , and x(i) represents the Al mole fraction x in the second composition layer 32 with respect to the i-th second composition layer 32 ⁇ i> as counted from the base substrate 1 side.
  • the composition modulation layer 3 has a configuration in which the Al mole fraction is lower in the second composition layer 32 ⁇ n> than in the second composition layer 32 ⁇ 1 > and, at least partially, the Al mole fraction x in the second composition layer 32 gradually decreases as the second composition layer 32 is more distant from the base substrate 1 . It is more preferable to satisfy the relationship of x(1) ⁇ 0.8 and x(n) ⁇ 0.2.
  • the expressions 1 and 2 are satisfied typically by forming the composition modulation layer 3 in such a manner that the second composition layer 32 more distant from the base substrate 1 has a lower Al mole fraction (that is, being richer in Ga). Therefore, hereinafter, in this embodiment, it is assumed that the second composition layer 32 more distant from the base substrate 1 has a lower Al mole fraction, including a case where there exist a second composition layer 32 ⁇ i ⁇ 1> and a second composition layer 32 ⁇ i> having the same Al mole fraction x.
  • forming the second composition layer 32 in such a manner is also expressed as giving a compositional grading to the second composition layer 32 .
  • the first composition layer 31 is made of AlN and the second composition layer 32 is made of a group-III nitride having a composition of Al x Ga 1-x N
  • the first composition layer 31 and the second composition layer 32 are formed so as to satisfy such a relationship that an in-plane lattice constant (lattice length) under a strain-free state (bulk state) is greater in the group-III nitride (Al x Ga 1-x N) of the latter than in the group-III nitride (AlN) of the former.
  • the second composition layer 32 is formed so as to be coherent to the first composition layer 31 .
  • each first composition layer 31 is formed with a thickness of about 3 nm to 20 nm, and typically 5 nm to 10 nm.
  • the second composition layer 32 is formed with a thickness of about 10 nm to 25 nm, and typically 15 nm to 35 nm.
  • the value of n is about 40 to 100.
  • the termination layer 4 is a layer formed with the same composition and the same thickness as those of the first composition layer 31 of the composition modulation layer 3 .
  • the termination layer 4 is substantially a part of the composition modulation layer 3 (the (n+1)th first composition layer 31 ⁇ n+1>).
  • the composition modulation layer 3 includes the termination layer 4 .
  • the buffer layer 5 has a configuration in which a first lamination unit and a second lamination unit are alternately and repeatedly laminated such that each of a lowermost portion and an uppermost portion of the buffer layer 5 is formed of the first lamination unit, when the layer made of AlN (the first composition layer 31 and the termination layer 4 ) is defined as the first lamination unit and the second composition layer 32 is defined as the second lamination unit.
  • the function layer 6 is at least one layer made of a group-III nitride and formed on the buffer layer 5 .
  • the function layer 6 is a layer that develops a predetermined function in a situation where predetermined semiconductor layers, electrodes, and the like, are additionally provided on the epitaxial substrate 10 to thereby form a semiconductor device. Accordingly, the function layer 6 is constituted of one or more layers having a composition and a thickness appropriate for this function.
  • FIG. 1 illustrates a case where the function layer 6 is constituted of a single layer, the configuration of the function layer 6 is not limited thereto.
  • a channel layer made of high-resistivity GaN and having a thickness of several tens nm and a barrier layer made of AlGaN, InAlN, or the like and having a thickness of several tens nm are laminated to serve as the function layer 6 , and thereby the epitaxial substrate 10 for a HEMT device is obtained. That is, a HEMT device is obtained by forming a gate electrode, a source electrode, and a drain electrode on the barrier layer, though not shown. For forming these electrodes, a known technique such as a photolithography process is applicable. In such a case, a spacer layer made of AlN and having a thickness of about 1 nm may be provided between the channel layer and the barrier layer.
  • a concentric Schottky diode is achieved by forming one group-III nitride layer (for example, a GaN layer) as the function layer 6 and foil ring an anode and a cathode thereon, though not shown.
  • group-III nitride layer for example, a GaN layer
  • the known technique such as the photolithography process is also applicable.
  • a (111) plane single crystal silicon wafer is prepared as the base substrate 1 .
  • a natural oxide film is removed by dilute hydrofluoric acid cleaning
  • SPM cleaning is performed to create a state where an oxide film having a thickness of about several ⁇ is formed on a wafer surface. This is set within a reactor of a MOCVD apparatus.
  • each layer is formed under predetermined heating conditions and a predetermined gas atmosphere.
  • a substrate temperature is maintained at a predetermined initial layer formation temperature of 800° C. or higher and 1200° C. or lower, and the pressure in the reactor is set to be about 0.1 to 30 kPa.
  • a TMA (trimethylaluminum) bubbling gas that is an aluminum raw material and a NH 3 gas are introduced into the reactor with an appropriate molar flow ratio.
  • a film formation speed is set to be 20 nm/min or higher, and a target film thickness is set to be 200 nm or less. Thereby, the formation of the first base layer 2 a is achieved.
  • a substrate temperature is maintained at a predetermined second base layer formation temperature of 800° C. or higher and 1200° C. or lower, and the pressure in the reactor is set to be 0.1 to 100 kPa.
  • a TMG (trimethylgallium) bubbling gas that is a gallium raw material, a TMA bubbling gas, and a NH 3 gas are introduced into the reactor with a predetermined flow ratio that is appropriate for a composition of the second base layer 2 b to be prepared.
  • TMG trimethylgallium
  • a substrate temperature is maintained at a predetermined formation temperature of 800° C. or higher and 1200° C. or lower that is appropriate for each of the layers, and the pressure in the reactor is maintained at a predetermined value of 0.1 to 100 kPa that is appropriate for each of the layers.
  • a NH 3 gas and a group-III nitride material gas are introduced into the reactor with a flow ratio that is appropriate for a composition to be achieved in each of the layers. Thereby, the formation of the respective layers is achieved.
  • TMA and TMG bubbling gases are introduced into the reactor with a flow ratio that is appropriate for a composition to be achieved in each of the layers.
  • a substrate temperature is maintained at a predetermined function layer formation temperature of 800° C. or higher and 1200° C. or lower, and the pressure in the reactor is set to be 0.1 to 100 kPa.
  • the pressure in the reactor is set to be 0.1 to 100 kPa.
  • at least one of a TMI bubbling gas, a TMA bubbling gas, and a TMG bubbling gas, and a NH 3 gas are introduced into the reactor with a flow ratio that is appropriate for a composition of the function layer 6 to be prepared.
  • NH 3 is reacted with at least one of TMI, TMA, and TMG.
  • the temperature of the epitaxial substrate 10 is lowered to an ordinary temperature. Then, the epitaxial substrate 10 is taken out from the reactor and subjected to an appropriate subsequent process (such as patterning of an electrode layer).
  • a tensile stress in an in-plane direction occurs in the crystal layer in the course of lowering the temperature to the ordinary temperature after the crystal growth, because the group-III nitride has a thermal expansion coefficient greater than that of silicon (for example, silicon: 3.4 ⁇ 10 ⁇ 6 /K, GaN: 5.5 ⁇ 10 ⁇ 6 /K). This tensile stress is a factor that causes occurrence of cracking and warping in the epitaxial substrate.
  • the buffer layer 5 is provided in the epitaxial substrate 10 for the purpose of reducing the tensile stress and suppressing occurrence of cracking and warping. More specifically, due to functions and effects exerted by the composition modulation layer 3 included in the buffer layer 5 , occurrence of cracking and warping in the epitaxial substrate 10 are suppressed. In the following, a detailed description will be given.
  • FIG. 2 is a model diagram showing a crystal lattice at a time when the second composition layer 32 is formed on the first composition layer 31 in the composition modulation layer 3 .
  • the lattice length, in the in-plane direction, of Al x Ga 1-x N of the second composition layer 32 under the strain-free state is defined as a 0
  • the actual lattice length thereof is defined as a.
  • a crystal growth progresses in the second composition layer 32 while keeping aligned with the crystal lattice of the first composition layer 31 .
  • the second composition layer 32 remains holding the strain energy (remains containing the compressive strain).
  • a crystal growth with the strain energy contained therein is referred to as a crystal growth in a coherent state.
  • the second composition layer 32 is in the coherent state relative to the first composition layer 31 as long as the second composition layer 32 is formed with a thickness smaller than a critical film thickness at which the strain energy is fully released.
  • the in-plane lattice constant of AlN of the first composition layer 31 is smaller than the in-plane lattice constant of Al x Ga 1-x N of the second composition layer 32 . Therefore, even when the first composition layer 31 is formed on the second composition layer 32 with the strain energy held therein, the coherent state is maintained, not causing a release of the strain energy held in the second composition layer 32 located immediately below. Then, if the second composition layer 32 is again grown on this first composition layer 31 so as to make the coherent state, the same compressive strain as described above is also caused in this second composition layer 32 , too.
  • the formation of the first composition layer 31 and the second composition layer 32 is alternately repeated while maintaining the growth in the coherent state.
  • the strain energy is held in each of the second composition layers 32 .
  • the composition modulation layer 3 is formed such that the (Expression 1) and (Expression 2) are satisfied, in other words, such that the second composition layer 32 ⁇ i> more distant from the base substrate 1 has a lower Al mole fraction x(i).
  • the difference between the in-plane lattice constant of Al x Ga 1-x N of the second composition layer 32 and the in-plane lattice constant of AlN of the first composition layers 31 that interpose the second composition layer 32 therebetween increases in a portion more distant from the base substrate 1 .
  • the composition modulation layer 3 can be considered as a strain-introduced layer configured such that a portion thereof located more distant from the base substrate 1 has a larger compressive strain contained therein.
  • This compressive strain acts in a direction exactly opposite to the direction of the tensile stress that is caused by a difference in the thermal expansion coefficient, and therefore functions to cancel the tensile stress at the time of temperature drop.
  • the tensile stress is cancelled by a force that is proportional to the total sum of the magnitudes of the compressive strains contained in the n second composition layers 32 .
  • the first composition layer 31 is interposed between the two second composition layers 32 .
  • the first composition layer 31 having too small a thickness is not preferable, because this reduces the compressive strain occurring in the second composition layer 32 , and rather, the tensile stress is likely to exist in the first composition layer 31 itself.
  • too large a thickness is not preferable, either, because the second composition layer 32 itself is likely to receive a force in a tensile direction.
  • the above-mentioned requirement that the thickness is about 3 to 20 nm is preferable in terms of not causing such failures.
  • the epitaxial substrate 10 including the buffer layer 5 configured in the above-described manner, due to the large compressive strain existing in the composition modulation layer 3 provided in the buffer layer 5 , a state is achieved in which a tensile stress caused by a difference in the thermal expansion coefficient between silicon and the group-III nitride is suitably cancelled. Thereby, in the epitaxial substrate 10 , a crack-free state is achieved and the amount of warping is suppressed to 100 ⁇ m or less.
  • n which represents the number of laminations of the first composition layer 31 and the second composition layer 32 , is about 40 to 100 and that the relationship of x(1) ⁇ 0.8 and x(n) ⁇ 0.2 is satisfied, are preferable in terms of providing a sufficient amount of compressive strain in the composition modulation layer 3 to thereby cancel the tensile stress caused by the difference in the thermal expansion coefficient.
  • the buffer layer 5 including the composition modulation layer 3 that serves as the strain-introduced layer is provided.
  • a crack-free state is achieved and warping is reduced.
  • the buffer layer 5 is formed on the second base layer 2 b in which an accumulation of strain energy is suppressed as described above, the effect of canceling the tensile stress is not hindered by any strain energy accumulated in the second base layer 2 b.
  • the configuration of the epitaxial substrate 10 according to this embodiment also contributes to increase of the breakdown voltage.
  • the epitaxial substrate 10 according to this embodiment is also characterized by high breakdown voltage properties because of providing of the buffer layer 5 (and more specifically the composition modulation layer 3 ) having the above-described configuration.
  • the breakdown voltage means a voltage value at which a leakage current of 1 mA/cm 2 occurs in a case where the voltage is applied to the epitaxial substrate 10 while being increased from 0V.
  • the epitaxial substrate 10 having a higher breakdown voltage can be obtained.
  • an epitaxial substrate in which the total film thickness of the entire epitaxial film is 5 ⁇ m and the breakdown voltage is 1000V or higher, and an epitaxial substrate in which the total film thickness of the entire epitaxial film is 7 ⁇ m and the breakdown voltage is 1400V or higher, can be achieved.
  • the buffer layer including the composition modulation layer is provided between the base substrate and the function layer, the composition modulation layer being formed by the first composition layer and the second composition layer being alternately laminated in such a manner that the Al mole fraction in the second composition layer decreases in an upper portion. Accordingly, a crack-free epitaxial substrate having an excellent crystal quality and excellent breakdown voltage properties can be obtained in which a silicon substrate, which is easily available in a large diameter at a low cost, is adopted as a base substrate thereof. In this epitaxial substrate, the amount of warping is suppressed to 100 ⁇ m or less.
  • an interface layer (not shown) may be provided between the base substrate 1 and the first base layer 2 a .
  • the interface layer has a thickness of about several nm and is made of amorphous SiAl u O v N w .
  • an interface layer is provided between the base substrate 1 and the first base layer 2 a , a lattice misfit between the base substrate 1 and the second base layer 2 b , and the like, is more effectively relieved, and the crystal quality of each layer formed thereon is further improved. That is, in a case where an interface layer is provided, an AlN layer that is the first base layer 2 a is formed such that the AlN layer has a concavo-convex shape similar to a case where no interface layer is provided and such that the amount of crystal grain boundaries existing therein is reduced as compared with the case where no interface layer is provided. Particularly, the first base layer 2 a having improvement in the half width value of the (0002) X-ray rocking curve is obtained.
  • the first base layer 2 a can be formed such that the half width of the (0002) X-ray rocking curve is in a range of 0.5 degrees or more and 0.8 degrees or less.
  • the function layer 6 can be formed with a more excellent crystal quality in which the half width of the (0002) X-ray rocking curve is 800 sec or less and the screw dislocation density is 1 ⁇ 10 9 /cm 2 or less.
  • the formation of the interface layer is achieved by, after the silicon wafer reaches the first base layer formation temperature and before the first base layer 2 a is formed, introducing only an TMA bubbling gas into the reactor to expose the wafer to an TMA bubbling gas atmosphere.
  • At least one of Si atoms and O atoms may diffuse and form a solid solution in the first base layer 2 a
  • at least one of N atoms and O atoms may diffuse and form a solid solution in the base substrate 1 .
  • Table 1 shows a basic configuration of the epitaxial substrates 10 according to the example, and more specifically, materials for forming the respective layers and the film thicknesses of the respective layers.
  • the materials and the film thicknesses of the base substrate 1 , the base layer 2 (the first base layer 2 a and the second base layer 2 b ), and the function layer 6 were the same for all the epitaxial substrates 10 .
  • the function layer 6 was configured as two layers of the channel layer and the barrier layer.
  • both the first composition layer 31 and the termination layer 4 were made of AlN, but their film thickness was different among specimens. In Table 1, this is indicated by the variable A (nm). Likewise, the film thickness of the second composition layer 32 is indicated by the variable B (inn). Here, n represents the number of each of the first composition layers 31 and the second composition layers 32 .
  • n second composition layers 32 were given the same Al mole fraction, and thereby eight types of epitaxial substrates 10 (specimens No. 15 to No. 22) in which no compositional grading was given to the second composition layers 32 were prepared.
  • the same preparation conditions as those of the example were adopted, except for the second composition layer 32 .
  • Table 2 shows, with respect to each specimen, the values of A, B, and n, the value of the Al mole fraction x(i) in the i-th one of the second composition layers 32 as counted from the base substrate 1 side, the total thickness of the composition modulation layer 3 , and the total thickness of the epitaxial film.
  • a specific process for preparing each of the epitaxial substrates 10 is as follows.
  • a (111) plane single crystal silicon wafer (hereinafter, a silicon wafer) of four inches having the p-type conductivity and having a substrate thickness of 525 ⁇ m was prepared as the base substrate 1 .
  • a NH 3 gas was introduced into the reactor, and the substrate surface was exposed to a NH 3 gas atmosphere for one minute.
  • a TMA bubbling gas was introduced into the reactor with a predetermined flow ratio, to react NH 3 with TMA, so that the first base layer 2 a whose surface has a three-dimensional concavo-convex shape was formed.
  • the growing speed (film formation speed) of the first base layer 2 a was set to be 20 nm/min, and the target average film thickness of the first base layer 2 a was set to be 100 nm.
  • the substrate temperature was set to be 1100° C. and the pressure in the reactor was set to be 15 kPa.
  • a TMG bubbling gas was further introduced into the reactor, to react NH 3 with TMA and TMG, so that an Al 0.1 Ga 0.9 N layer serving as the second base layer 2 b was formed so as to have an average film thickness of about 40 nm.
  • the buffer layer 5 and more specifically, the composition modulation layer 3 and the termination layer 4 , were prepared in accordance with the values of A, B, n, and x(i) shown in Table 2.
  • example (5 nm, 7.5 nm, 10 nm), comparative example (5 nm);
  • n example (45, 50, 60, 70, 80, 90, 100), comparative example (50, 70, 80, 100).
  • the substrate temperature was set to be 1100° C.
  • the pressure in the reactor was set to be 15 kPa.
  • the same material gas as for the formation of the base layer 2 was used.
  • FIG. 3 is a diagram illustrating how the Al mole fraction was changed in main specimens. It is to be noted that any specimen was formed so as to satisfy the relationship of x(1) ⁇ 0.8 and x(n) ⁇ 0.2.
  • the value of the Al mole fraction x in the second composition layer 32 was set to be any of 0, 0.1, 0.2, 0.3, and 0.4.
  • the channel layer made of GaN and serving as the function layer 6 was formed with a thickness of 700 nm, and then the barrier layer made of Al 0.2 Ga 0.8 N was further formed with a thickness of 25 nm.
  • the substrate temperature was set to be 1100° C., and the pressure in the reactor was set to be 15 kPa. The same material gas as for the formation of the base layer 2 was used.
  • the presence or absence of occurrence of cracking was visually checked. Additionally, the amount of warping was measured using a laser displacement gauge. Here, for the epitaxial substrates 10 where cracking occurred, the breakdown voltage was measured in a region not including the cracking. Results of the measurements are shown in Table 3.
  • the amount of warping was at least 135 ⁇ m, which largely exceeds 100 ⁇ m, while in the specimens according to the example where no cracking occurred, the amount of warping was suppressed to about 60 ⁇ m to 70 ⁇ m.
  • composition modulation layer 3 by alternately laminating the first composition layer 31 and the second composition layer 32 in such a manner that the compositional grading is given to the second composition layer 32 as described in the example, is effective in achieving a crack-free state of the epitaxial substrate 10 and suppression of warping therein.
  • the second composition layer has a relatively small thickness, and therefore it would be guessed that the second composition layer itself grew in a coherent state. Despite this, cracking occurred in the comparative example. Accordingly, it is considered that, in a case where, as in the comparative example, the first composition layer and the second composition layer are merely alternately laminated without any compositional grading given to the second composition layer, the compressive strain is introduced into each individual second composition layer 32 but the total sum thereof is not sufficient for canceling the tensile stress.
  • the breakdown voltage in the specimens according to the comparative example, even the highest breakdown voltage was below 600V, whereas in all the specimens according to the example, the breakdown voltage was 600V or higher.

Abstract

Provided is a crack-free epitaxial substrate having excellent breakdown voltage properties in which a silicon substrate is used as a base substrate thereof. The epitaxial substrate includes: a (111) single crystal Si substrate and a buffer layer including a composition modulation layer that is formed of a first composition layer made of AlN and a second composition layer made of AlxGa1-xN (0≦x<1) being alternately laminated. The relationship of x(1)≧x(2)≧ . . . ≧x(n−1)≧x(n) and x(1)>x(n) is satisfied, where n represents the number of laminations of each of the first and the second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of the second composition layers as counted from the base substrate side, to thereby cause a compressive strain to exist such that the compressive strain increases in a portion more distant from the base substrate.

Description

    TECHNICAL FIELD
  • The present invention relates to an epitaxial substrate for use in a semiconductor device, and particularly to an epitaxial substrate made of a group-III nitride.
    • BACKGROUND ART
  • A nitride semiconductor is attracting attention as a semiconductor material for a light-emitting device such as a LED or a LD and for a high-frequency/high-power electronic device such as a HEMT, because the nitride semiconductor has a wide band gap of direct transition type and the breakdown electric field and the saturation electron velocity thereof are high. For example, a HEMT (high electron mobility transistor) device in which a barrier layer made of AlGaN and a channel layer made of GaN are laminated takes advantage of the feature that causes a high-concentration two-dimensional electron gas (2DEG) to occur in a lamination interface (hetero interface) due to the large polarization effect (a spontaneous polarization effect and a piezo polarization effect) specific to a nitride material (for example, see Non-Patent Document 1).
  • In some cases, a single crystal (a different kind single crystal) having a composition different from that of a group-III nitride, such as SiC, is used as a base substrate for use in a HEMT-device epitaxial substrate. In this case, a buffer layer such as a strained-superlattice layer or a low-temperature growth buffer layer is generally formed as an initially-grown layer on the base substrate. Accordingly, a configuration in which a barrier layer, a channel layer, and a buffer layer are epitaxially formed on a base substrate is the most basic configuration of the HEMT-device substrate including a base substrate made of a different kind single crystal. Additionally, a spacer layer having a thickness of about 1 nm may be sometimes provided between the barrier layer and the channel layer, for the purpose of facilitating a spatial confinement of the two-dimensional electron gas. The spacer layer is made of, for example, AlN. Moreover, a cap layer made of, for example, an n-type GaN layer or a superlattice layer may be sometimes formed on the barrier layer, for the purpose of controlling the energy level at the most superficial surface of the HEMT-device substrate and improving contact characteristics of contact with an electrode.
  • The HEMT device and the HEMT-device substrate involve various problems including problems concerning improvement of the performance such as increasing the power density and efficiency, problems concerning improvement of the functionality such as a normally-off operation, fundamental problems concerning a high reliability and cost reduction, and the like. Active efforts are made on each of the problems.
  • On the other hand, in the preparation of the above-mentioned nitride device, research and development have been made about the use of single crystal silicon for a base substrate for the purpose of reduction of the cost of an epitaxial substrate, furthermore, integration with a silicon-based circuit device, and the like (for example, see Patent Documents 1 to 3, and Non-Patent Document 2). In a case where a conductive material such as silicon is selected for the base substrate of the HEMT-device epitaxial substrate, a field plate effect is applied from a back surface of the base substrate, and therefore a HEMT device can be designed for a high breakdown voltage and high-speed switching.
  • It is already known that, in order that the HEMT-device epitaxial substrate can be structured with a high breakdown voltage, it is effective to increase the total film thickness of the channel layer and the barrier layer and to improve the electrical breakdown strength of both of the layers (for example, see Non-Patent Document 2).
  • A method for manufacturing a semiconductor device is also known in which an interposed layer made of AlN is formed on a Si base substrate, then a first semiconductor layer made of GaN and a second semiconductor layer made of AlN are alternately formed so as to cause convex warping as a whole, and then these layers are made contract at a subsequent temperature drop, to result in cancellation of the warping of the entire substrate (for example, see Patent Document 4).
  • However, it is known that forming a nitride film of good quality on a silicon substrate is very difficult as compared with a case of using a sapphire substrate or a SiC substrate, for the following reasons.
  • Firstly, the values of the lattice constants of silicon and nitride materials are greatly different from each other. This causes a misfit dislocation at an interface between the silicon substrate and a growth film, and facilitates a three-dimensional growth mode at a timing from the nucleus formation to the growth. In other words, this is a factor that hinders the formation of a good nitride epitaxial film having a low dislocation density and a flat surface.
  • Additionally, the nitride material has a higher thermal expansion coefficient value than that of silicon. Therefore, in the step of lowering the temperature to the vicinity of the room temperature after a nitride film is epitaxially grown on the silicon substrate at a high temperature, a tensile stress acts in the nitride film. As a result, it is likely that cracking occurs in a film surface and large warping occurs in the substrate.
  • Moreover, it is also known that trimethylgallium (TMG) that is a material gas of the nitride material for a vapor-phase growth is likely to form a liquid-phase compound with silicon, which is a factor that hinders the epitaxial growth.
  • In a case where the conventional techniques disclosed in the Patent Documents 1 to 3 and in the Non-Patent Document 1 are adopted, it is possible to cause an epitaxial growth of a GaN film on the silicon substrate. However, the resulting GaN film never has a better crystal quality as compared with a case of using SiC or sapphire for the base substrate. Therefore, preparing an electronic device such as a HEMT using the conventional techniques involves problems of a low electron mobility, a leakage current during the off-time, and a low breakdown voltage.
  • Furthermore, in the method disclosed in the Patent Document 4, large convex warping is intentionally caused in the course of the device preparation. This may cause cracking in the course of the device preparation, depending on conditions under which the layers are formed.
    • PRIOR-ART DOCUMENTS Patent Documents
    • Patent Document 1: Japanese Patent Application Laid-Open No. 10-163528 (1998)
    • Patent Document 2: Japanese Patent Application Laid-Open No. 2004-349387
    • Patent Document 3: Japanese Patent Application Laid-Open No. 2005-350321
    • Patent Document 4: Japanese Patent Application Laid-Open No. 2009-289956
    Non-Patent Documents
    • Non-Patent Document 1: “Highly Reliable 250W GaN High Electron Mobility Transistor Power Amplifier”, Toshihide Kikkawa, Jpn. J. Appl. Phys. 44, (2005), 4896.
    • Non-Patent Document 2: “High power AlGaN/GaN HFET with a high breakdown voltage of over 1.8 kV on 4 inch Si substrates and the suppression of current collapse”, Nariaki Ikeda, Syuusuke Kaya, Jiang Li, Yoshihiro Sato, Sadahiro Kato, Seikoh Yoshida, Proceedings of the 20th International Symposium on Power Semiconductor Devices & IC's May 18-22, 2008 Orlando, Fla.”, pp. 287-290
    SUMMARY OF THE INVENTION
  • The present invention has been made in view of the problems described above, and an object of the present invention is to provide a crack-free epitaxial substrate having excellent breakdown voltage properties in which a silicon substrate is used as a base substrate.
  • To solve the problems described above, a first aspect of the present invention is an epitaxial substrate in which a group of group-III nitride layers are formed on a base substrate made of (111)-oriented single crystal silicon such that a (0001) crystal plane of the group of group-III nitride layers is substantially in parallel with a substrate surface of the base substrate. The epitaxial substrate includes: a buffer layer including a composition modulation layer that is formed of a first composition layer made of AlN and a second composition layer made of a group-III nitride having a composition of AlxGa1-xN (0≦x<1) being alternately laminated; and a crystal layer formed on the buffer layer. The composition modulation layer is formed so as to satisfy the relationship of x(1)≧x(2)≧ . . . ≧x(n−1)≧x(n) and x(1)>x(n), where n represents the number of laminations of each of the first composition layer and the second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of the second composition layers as counted from the base substrate side, to thereby cause a compressive strain to exist in the composition modulation layer such that the compressive strain increases in a portion more distant from the base substrate.
  • In a second aspect of the present invention, in the epitaxial substrate according to the first aspect, each of the second composition layers is formed so as to be in a coherent state relative to the first composition layer.
  • In a third aspect of the present invention, the epitaxial substrate according to the first aspect further includes: a first base layer made of AlN and formed on the base substrate; and a second base layer made of AlpGa1-pN (0≦p<1) and formed on the first base layer. The first base layer is a layer with many crystal defects configured of at least one kind from a columnar or granular crystal or domain. An interface between the first base layer and the second base layer defines a three-dimensional concavo-convex surface. The buffer layer is formed immediately on the second base layer.
  • A fourth aspect of the present invention is a method for manufacturing an epitaxial substrate for use in a semiconductor device, the epitaxial substrate having a group of group-III nitride layers formed on a base substrate made of (111)-oriented single crystal silicon such that a (0001) crystal plane of the group of group-III nitride layers is substantially in parallel with a substrate surface of the base substrate. The method includes: a buffer layer formation step for forming a buffer layer; and a crystal layer formation step for forming a crystal layer above the buffer layer, the crystal layer being made of a group-III nitride. The buffer layer formation step includes a composition modulation layer formation step for forming a composition modulation layer by alternately laminating a first composition layer made of AlN and a second composition layer made of a group-III nitride having a composition of AlxGa1-xN (0≦x<1). In the composition modulation layer formation step, the composition modulation layer is formed in such a manner that: the relationship of x(1)≧x(2)≧ . . . ≧x(n−1)≧x(n) and x(1)>x(n) is satisfied, where n represents the number of laminations of each of the first composition layer and the second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of the second composition layers as counted from the base substrate side; and each of the second composition layers is in a coherent state relative to the first composition layer.
  • In a fifth aspect of the present invention, the method for manufacturing the epitaxial substrate according to the fourth aspect further includes: a first base layer formation step for forming a first base layer on the base substrate, the first base layer being made of AlN; and a second base layer formation step for forming a second base layer on the first base layer, the second base layer being made of AlGa1-pN (0≦p<1). In the first base layer formation step, the first base layer is formed as a layer with many crystal defects configured of at least one kind from a columnar or granular crystal or domain, such that a surface thereof is a three-dimensional concavo-convex surface. In the composition modulation layer formation step, the composition modulation layer is formed immediately on the second base layer.
  • In the first to fifth aspects of the present invention, the compressive strain exists in the buffer layer. Accordingly, a tensile stress caused by a difference in a thermal expansion coefficient between silicon and a group-III nitride is cancelled by the compressive strain. Therefore, a crack-free epitaxial substrate having a small amount of warping and an excellent crystal quality and excellent breakdown voltage properties can be obtained even when a silicon substrate is used as the base substrate.
  • Particularly, in the third and fifth aspects, the buffer layer is provided on the base layer having a low dislocation and an excellent surface flatness. Accordingly, the buffer layer, the crystal layer, and the like, have good crystal quality. On the other hand, an accumulation of strain energy in the second base layer is suppressed. Therefore, the effect of canceling the tensile stress exerted by the compressive strain existing in the buffer layer is not hindered by any accumulation of strain energy in the base layer.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a schematic cross-sectional view showing an outline configuration of an epitaxial substrate 10 according to an embodiment of the present invention.
  • FIGS. 2A, 2B and 2C are model diagrams showing a crystal lattice at a time when a second composition layer 32 is formed on a first composition layer 31 in a composition modulation layer 3.
  • FIG. 3 is a diagram illustrating how the Al mole fraction was changed in main specimens of examples.
    •  EMBODIMENT FOR CARRYING OUT THE INVENTION
  • <Outline Configuration of Epitaxial Substrate>
  • FIG. 1 is a schematic cross-sectional view showing an outline configuration of an epitaxial substrate 10 according to an embodiment of the present invention. The epitaxial substrate 10 mainly includes a base substrate 1, a base layer 2, a buffer layer 5, and a function layer 6. The buffer layer 5 includes a composition modulation layer 3 and a termination layer 4. In the following, the layers formed on the base substrate 1 will be sometimes collectively referred to as an epitaxial film. Here, for convenience of the description, the proportion of existence of Al in the group-III elements will be sometimes referred to as Al mole fraction.
  • The base substrate 1 is a wafer of (111) plane single crystal silicon having the p-type conductivity. The thickness of the base substrate 1 is not particularly limited, but for convenience of handling, it is preferable to use the base substrate 1 having a thickness of several hundred μm to several mm.
  • Each of the base layer 2, the composition modulation layer 3, the termination layer 4, and the function layer 6 is a layer formed of a wurtzite-type group-III nitride by using an epitaxial growth method such that a its (0001) crystal plane can be substantially in parallel with a substrate surface of the base substrate 1. In a preferred example, these layers are formed by a metalorganic chemical vapor deposition method (MOCVD method).
  • The base layer 2 is a layer provided for the purpose of enabling each of the above-mentioned layers to be formed thereon with a good crystal quality. To be specific, the base layer 2 is formed in such a manner that its dislocation density is suitably reduced and it has a good crystal quality at least near its surface (near an interface with the composition modulation layer 3). As a result, a good crystal quality is obtained in the composition modulation layer 3, and additionally in the layers formed thereon.
  • In this embodiment, to satisfy the purpose, the base layer 2 is composed of a first base layer 2 a and a second base layer 2 b, as described below.
  • The first base layer 2 a is a layer made of AlN. The first base layer 2 a is a layer configured of a large number of small columnar crystals or the like (at least one kind from columnar crystals, granular crystals, columnar domains, and granular domains) that have been grown in a direction (film formation direction) substantially perpendicular to the substrate surface of the base substrate 1. In other words, the first base layer 2 a is a layer with many defects having inferior crystal properties, in which, although uniaxial orientation is achieved along a lamination direction of the epitaxial substrate 10, many crystal grain boundaries or dislocations exist along the lamination direction. In this embodiment, for convenience of the description, the crystal grain boundary is sometimes used as the term inclusive of domain grain boundaries and dislocations, too. In the first base layer 2 a, the interval of the crystal grain boundaries is at most about several tens nm.
  • The first base layer 2 a having this configuration is formed such that the half width of a (0002) X-ray rocking curve can be 0.5 degrees or more and 1.1 degrees or less and such that the half width of a (10-10) X-ray rocking curve can be 0.8 degrees or more and 1.1 degrees or less. The half width of the (0002) X-ray rocking curve serves as an index of the magnitude of mosaicity of a c-axis tilt component or the frequency of screw dislocations. The half width of the (10-10) X-ray rocking curve serves as an index of the magnitude of mosaicity of a crystal rotation component whose rotation axis is c-axis or the frequency of edge dislocations.
  • On the other hand, the second base layer 2 b is a layer formed on the first base layer 2 a and made of a group-III nitride having a composition of AlpGa1-pN (0≦p<1).
  • An interface I1 (a surface of the first base layer 2 a) between the first base layer 2 a and the second base layer 2 b is a three-dimensional concavo-convex surface that reflects the outer shapes of the columnar crystals and the like included in the first base layer 2 a. The fact that the interface I1 has such a shape is clearly confirmed in, for example, a HAADF (high-angle annular dark-field) image of the epitaxial substrate 10. The HAADF image is obtained by a scanning transmission electron microscope (STEM), and is a mapping image of the integrated intensity of electron that is inelastically scattered at a high angle. In the HAADF image, the image intensity is proportional to the square of an atomic number, and a portion where an atom having a greater atomic number exists is observed more brightly (more white). Therefore, the second base layer 2 b containing Ga is observed relatively bright, and the first base layer 2 a not containing Ga is observed relatively dark. Thereby, the fact that the interface I1 therebetween is configured as a three-dimensional concavo-convex surface is easily recognized.
  • In the schematic cross-section of FIG. 1, convex portions 2 c of the first base layer 2 a are located at substantially regular intervals. This is merely for convenience of illustration. Actually, the convex portions 2 c are not necessarily located at regular intervals. Preferably, the first base layer 2 a is formed such that the density of the convex portions 2 c can be 5×109/cm2 or more and 5×1010/cm2 or less and the average interval of the convex portions 2 c can be 45 nm or more and 140 nm or less. When these ranges are satisfied, the function layer 6 having, particularly, an excellent crystal quality can be formed. In this embodiment, the convex portion 2 c of the first base layer 2 a always denotes a position substantially at the apex of an upward convex portion of the surface (interface I1). From the results of experiments and observations made by the inventors of the present invention, it has been confirmed that a side wall of the convex portion 2 c is formed by a (10-11) plane or (10-12) plane of AlN.
  • In order that the convex portions 2 c that satisfy the above-mentioned density and average interval can be formed on the surface of the first base layer 2 a, it is preferable to form the first base layer 2 a with an average film thickness of 40 nm or more and 200 nm or less. In a case where the average film thickness is less than 40 nm, it is difficult to achieve a state where the substrate surface is thoroughly covered with AlN while forming the convex portions 2 c as described above. On the other hand, when the average film thickness exceeds 200 nm, flattening of an AlN surface starts to progress, to make it difficult to form the convex portions 2 c described above.
  • The formation of the first base layer 2 a is performed under predetermined epitaxial growth conditions. Here, forming the first base layer 2 a with AlN is preferable in terms of not containing Ga which forms a liquid-phase compound with silicon and in terms of easily configuring the interface I1 as a three-dimensional concavo-convex surface because a horizontal growth is relatively unlikely to progress.
  • In the epitaxial substrate 10, the first base layer 2 a that is a layer with many defects in which the crystal grain boundaries exist is interposed between the base substrate 1 and the second base layer 2 b in the above-described manner. This relieves a lattice misfit between the base substrate 1 and the second base layer 2 b, and thus an accumulation of strain energy caused by this lattice misfit is suppressed. The above-described ranges of the half widths of the (0002) and (10-10) X-ray rocking curves with respect to the first base layer 2 a are set as ranges that can suitably suppress the accumulation of strain energy due to the crystal grain boundaries.
  • However, the interposition of the first base layer 2 a causes an enormous number of dislocations originating from the crystal grain boundaries such as the columnar crystals of the first base layer 2 a to propagate in the second base layer 2 b. In this embodiment, as described above, the interface I1 between the first base layer 2 a and the second base layer 2 b is configured as a three-dimensional concavo-convex surface, and thereby such dislocations are effectively reduced.
  • Since the interface I1 between the first base layer 2 a and the second base layer 2 b is configured as a three-dimensional concavo-convex surface, most of the dislocations caused in the first base layer 2 a are bent at the interface I1 during the propagation (penetration) from the first base layer 2 a to the second base layer 2 b, and coalesce and disappear within the second base layer 2 b. As a result, only a small part of the dislocations originating from the first base layer 2 a penetrates through the second base layer 2 b.
  • Preferably, although the second base layer 2 b is formed along the shape of the surface of the first base layer 2 a (the shape of the interface I1) in an initial stage of the growth, the surface thereof is gradually flattened along with the progress of the growth, and finally obtains a surface roughness of 10 nm or less. In this embodiment, the surface roughness is expressed as an average roughness ra in a region of 5 μm×5 μm which has been measured by an AFM (atomic force microscope). Here, in terms of obtaining a good surface flatness of the second base layer 2 b, it is preferable that the second base layer 2 b is formed of a group-III nitride having a composition that contains at least Ga, which allows a horizontal growth to progress relatively easily.
  • It is preferable that the second base layer 2 b has an average thickness of 40 nm or more. This is because, when the average thickness is less than 40 nm, such problems arise that concaves and convexes caused by the first base layer 2 a cannot sufficiently be flattened, and that the disappearance of dislocations having propagated to the second base layer 2 b and coalesced with each other does not sufficiently occur. In a case where the average thickness is 40 nm or more, the reduction of the dislocation density and the flattening of the surface are effectively achieved. Therefore, in a technical sense, no particular limitation is put on an upper limit of the thickness of the second base layer 2 b, but from the viewpoint of the productivity, it is preferable that the thickness is about several μm or less.
  • As described above, the surface of the second base layer 2 b has a low dislocation and an excellent flatness, and therefore the layers formed thereon have a good crystal quality.
  • The composition modulation layer 3 is a part formed by a first composition layer 31 made of AlN and a second composition layer 32 made of a group-III nitride having a composition of AlxGa1-xN (0≦x<1) being alternately laminated. In this embodiment, the i-th first composition layer 31 as counted from the base substrate 1 side is expressed as “31<i>”, and the i-th second composition layer 32 as counted from the base substrate 1 side is expressed as “32<i>”.
  • The second composition layer 32 is formed so as to satisfy the following expressions 1 and 2, where n (n is a natural number equal to or greater than two) represents the number of the first composition layers 31 and the number of the second composition layers 32, and x(i) represents the Al mole fraction x in the second composition layer 32 with respect to the i-th second composition layer 32<i> as counted from the base substrate 1 side.

  • x(1)≧x(2)≧ . . . ≧x(n−1)≧x(n)  (Expression 1)

  • x(1)<x(n)  (Expression 2)
  • That is, the composition modulation layer 3 has a configuration in which the Al mole fraction is lower in the second composition layer 32<n> than in the second composition layer 32<1> and, at least partially, the Al mole fraction x in the second composition layer 32 gradually decreases as the second composition layer 32 is more distant from the base substrate 1. It is more preferable to satisfy the relationship of x(1)≧0.8 and x(n)≦0.2.
  • The expressions 1 and 2 are satisfied typically by forming the composition modulation layer 3 in such a manner that the second composition layer 32 more distant from the base substrate 1 has a lower Al mole fraction (that is, being richer in Ga). Therefore, hereinafter, in this embodiment, it is assumed that the second composition layer 32 more distant from the base substrate 1 has a lower Al mole fraction, including a case where there exist a second composition layer 32<i−1> and a second composition layer 32<i> having the same Al mole fraction x. Here, forming the second composition layer 32 in such a manner is also expressed as giving a compositional grading to the second composition layer 32.
  • Since the first composition layer 31 is made of AlN and the second composition layer 32 is made of a group-III nitride having a composition of AlxGa1-xN, the first composition layer 31 and the second composition layer 32 are formed so as to satisfy such a relationship that an in-plane lattice constant (lattice length) under a strain-free state (bulk state) is greater in the group-III nitride (AlxGa1-xN) of the latter than in the group-III nitride (AlN) of the former.
  • Additionally, in the composition modulation layer 3, the second composition layer 32 is formed so as to be coherent to the first composition layer 31.
  • It is preferable that each first composition layer 31 is formed with a thickness of about 3 nm to 20 nm, and typically 5 nm to 10 nm. On the other hand, it is preferable that the second composition layer 32 is formed with a thickness of about 10 nm to 25 nm, and typically 15 nm to 35 nm. The value of n is about 40 to 100.
  • The termination layer 4 is a layer formed with the same composition and the same thickness as those of the first composition layer 31 of the composition modulation layer 3. Thus, it can be said that the termination layer 4 is substantially a part of the composition modulation layer 3 (the (n+1)th first composition layer 31<n+1>). Hereinafter, if not otherwise specified, it is assumed that the composition modulation layer 3 includes the termination layer 4. Therefore, it can be said that the buffer layer 5 has a configuration in which a first lamination unit and a second lamination unit are alternately and repeatedly laminated such that each of a lowermost portion and an uppermost portion of the buffer layer 5 is formed of the first lamination unit, when the layer made of AlN (the first composition layer 31 and the termination layer 4) is defined as the first lamination unit and the second composition layer 32 is defined as the second lamination unit.
  • The function layer 6 is at least one layer made of a group-III nitride and formed on the buffer layer 5. The function layer 6 is a layer that develops a predetermined function in a situation where predetermined semiconductor layers, electrodes, and the like, are additionally provided on the epitaxial substrate 10 to thereby form a semiconductor device. Accordingly, the function layer 6 is constituted of one or more layers having a composition and a thickness appropriate for this function. Although FIG. 1 illustrates a case where the function layer 6 is constituted of a single layer, the configuration of the function layer 6 is not limited thereto.
  • For example, a channel layer made of high-resistivity GaN and having a thickness of several tens nm and a barrier layer made of AlGaN, InAlN, or the like and having a thickness of several tens nm are laminated to serve as the function layer 6, and thereby the epitaxial substrate 10 for a HEMT device is obtained. That is, a HEMT device is obtained by forming a gate electrode, a source electrode, and a drain electrode on the barrier layer, though not shown. For forming these electrodes, a known technique such as a photolithography process is applicable. In such a case, a spacer layer made of AlN and having a thickness of about 1 nm may be provided between the channel layer and the barrier layer.
  • Alternatively, a concentric Schottky diode is achieved by forming one group-III nitride layer (for example, a GaN layer) as the function layer 6 and foil ring an anode and a cathode thereon, though not shown. For forming these electrodes, the known technique such as the photolithography process is also applicable.
  • <Method for Manufacturing Epitaxial Substrate>
  • Next, a method for manufacturing the epitaxial substrate 10 will be generally described while a case of using the MOCVD method is taken as an example.
  • Firstly, a (111) plane single crystal silicon wafer is prepared as the base substrate 1. A natural oxide film is removed by dilute hydrofluoric acid cleaning Then, SPM cleaning is performed to create a state where an oxide film having a thickness of about several Å is formed on a wafer surface. This is set within a reactor of a MOCVD apparatus.
  • Then, each layer is formed under predetermined heating conditions and a predetermined gas atmosphere. Firstly, for the first base layer 2 a made of AlN, a substrate temperature is maintained at a predetermined initial layer formation temperature of 800° C. or higher and 1200° C. or lower, and the pressure in the reactor is set to be about 0.1 to 30 kPa. In this state, a TMA (trimethylaluminum) bubbling gas that is an aluminum raw material and a NH3 gas are introduced into the reactor with an appropriate molar flow ratio. A film formation speed is set to be 20 nm/min or higher, and a target film thickness is set to be 200 nm or less. Thereby, the formation of the first base layer 2 a is achieved.
  • For the formation of the second base layer 2 b, after the formation of the first base layer 2 a, a substrate temperature is maintained at a predetermined second base layer formation temperature of 800° C. or higher and 1200° C. or lower, and the pressure in the reactor is set to be 0.1 to 100 kPa. In this state, a TMG (trimethylgallium) bubbling gas that is a gallium raw material, a TMA bubbling gas, and a NH3 gas are introduced into the reactor with a predetermined flow ratio that is appropriate for a composition of the second base layer 2 b to be prepared. Thus, NH3 is reacted with TMA and TMG. Thereby, the formation of the second base layer 2 b is achieved.
  • For the formation of the respective layers included in the buffer layer 5, that is, for the formation of the first composition layer 31 and the second composition layer 32 included in the composition modulation layer 3 and the termination layer 4, subsequent to the formation of the second base layer 2 b, a substrate temperature is maintained at a predetermined formation temperature of 800° C. or higher and 1200° C. or lower that is appropriate for each of the layers, and the pressure in the reactor is maintained at a predetermined value of 0.1 to 100 kPa that is appropriate for each of the layers. In this state, a NH3 gas and a group-III nitride material gas (TMA and TMG bubbling gases) are introduced into the reactor with a flow ratio that is appropriate for a composition to be achieved in each of the layers. Thereby, the formation of the respective layers is achieved. At this time, by changing the flow ratio at a timing appropriate for a set film thickness, the respective layers are formed in a continuous manner and with desired film thicknesses.
  • For the formation of the function layer 6, after the formation of the buffer layer 5, a substrate temperature is maintained at a predetermined function layer formation temperature of 800° C. or higher and 1200° C. or lower, and the pressure in the reactor is set to be 0.1 to 100 kPa. In this state, at least one of a TMI bubbling gas, a TMA bubbling gas, and a TMG bubbling gas, and a NH3 gas are introduced into the reactor with a flow ratio that is appropriate for a composition of the function layer 6 to be prepared. Thus, NH3 is reacted with at least one of TMI, TMA, and TMG. Thereby, the formation of the function layer 6 is achieved.
  • After the function layer 6 is formed, in the reactor, the temperature of the epitaxial substrate 10 is lowered to an ordinary temperature. Then, the epitaxial substrate 10 is taken out from the reactor and subjected to an appropriate subsequent process (such as patterning of an electrode layer).
  • <Functions and Effects of Buffer Layer>
  • Generally, as is the case for this embodiment as well, in a case of preparing an epitaxial substrate by causing a crystal layer made of a group-III nitride to epitaxially grow on a single crystal silicon wafer at a predetermined formation temperature, a tensile stress in an in-plane direction occurs in the crystal layer in the course of lowering the temperature to the ordinary temperature after the crystal growth, because the group-III nitride has a thermal expansion coefficient greater than that of silicon (for example, silicon: 3.4×10−6/K, GaN: 5.5×10−6/K). This tensile stress is a factor that causes occurrence of cracking and warping in the epitaxial substrate. In this embodiment, the buffer layer 5 is provided in the epitaxial substrate 10 for the purpose of reducing the tensile stress and suppressing occurrence of cracking and warping. More specifically, due to functions and effects exerted by the composition modulation layer 3 included in the buffer layer 5, occurrence of cracking and warping in the epitaxial substrate 10 are suppressed. In the following, a detailed description will be given.
  • FIG. 2 is a model diagram showing a crystal lattice at a time when the second composition layer 32 is formed on the first composition layer 31 in the composition modulation layer 3. Here, the lattice length, in the in-plane direction, of AlxGa1-xN of the second composition layer 32 under the strain-free state is defined as a0, and the actual lattice length thereof is defined as a. In this embodiment, as shown in FIGS. 2A and 2B, a crystal growth progresses in the second composition layer 32 while keeping aligned with the crystal lattice of the first composition layer 31. This means that a compressive strain of s=a0−a occurs in the in-plane direction of the second composition layer 32 during the crystal growth. That is, the crystal growth of the second composition layer 32 progresses with strain energy held therein.
  • As the growth advances, energy instability increases. Therefore, a misfit dislocation is gradually introduced in the second composition layer 32, for releasing the strain energy. Then, upon reaching a certain critical state, the strain energy held in the second composition layer 32 is fully released. At this time, a state of a=a0 is created as shown in FIG. 2C.
  • However, if the formation of the second composition layer 32 is terminated in a state of a0>a as shown in FIG. 2B prior to reaching the state shown in FIG. 2C, the second composition layer 32 remains holding the strain energy (remains containing the compressive strain). In this embodiment, such a crystal growth with the strain energy contained therein is referred to as a crystal growth in a coherent state. In other words, the second composition layer 32 is in the coherent state relative to the first composition layer 31 as long as the second composition layer 32 is formed with a thickness smaller than a critical film thickness at which the strain energy is fully released. Alternatively, in still other words, the second composition layer 32 is in the coherent state relative to the first composition layer 31 as long as the lattice length a of the uppermost surface of the second composition layer 32 (the surface that will be in contact with the first composition layer 31 located immediately above) satisfies a0>a. Even if a0=a is created partially in the second composition layer 32, it can be said that the second composition layer 32 is in the coherent state relative to the first composition layer 31, as long as the second composition layer 32 contains the strain energy in the above-described manner.
  • The in-plane lattice constant of AlN of the first composition layer 31 is smaller than the in-plane lattice constant of AlxGa1-xN of the second composition layer 32. Therefore, even when the first composition layer 31 is formed on the second composition layer 32 with the strain energy held therein, the coherent state is maintained, not causing a release of the strain energy held in the second composition layer 32 located immediately below. Then, if the second composition layer 32 is again grown on this first composition layer 31 so as to make the coherent state, the same compressive strain as described above is also caused in this second composition layer 32, too.
  • Subsequently, in the same manner, the formation of the first composition layer 31 and the second composition layer 32 is alternately repeated while maintaining the growth in the coherent state. Thereby, the strain energy is held in each of the second composition layers 32. Moreover, in this embodiment, the composition modulation layer 3 is formed such that the (Expression 1) and (Expression 2) are satisfied, in other words, such that the second composition layer 32<i> more distant from the base substrate 1 has a lower Al mole fraction x(i). Therefore, the difference between the in-plane lattice constant of AlxGa1-xN of the second composition layer 32 and the in-plane lattice constant of AlN of the first composition layers 31 that interpose the second composition layer 32 therebetween increases in a portion more distant from the base substrate 1. As a result, as the second composition layer 32 is formed upper, a larger compressive strain is contained therein. Accordingly, the composition modulation layer 3 can be considered as a strain-introduced layer configured such that a portion thereof located more distant from the base substrate 1 has a larger compressive strain contained therein.
  • This compressive strain acts in a direction exactly opposite to the direction of the tensile stress that is caused by a difference in the thermal expansion coefficient, and therefore functions to cancel the tensile stress at the time of temperature drop. In outline, the tensile stress is cancelled by a force that is proportional to the total sum of the magnitudes of the compressive strains contained in the n second composition layers 32.
  • The first composition layer 31 is interposed between the two second composition layers 32. The first composition layer 31 having too small a thickness is not preferable, because this reduces the compressive strain occurring in the second composition layer 32, and rather, the tensile stress is likely to exist in the first composition layer 31 itself. On the other hand, too large a thickness is not preferable, either, because the second composition layer 32 itself is likely to receive a force in a tensile direction. The above-mentioned requirement that the thickness is about 3 to 20 nm is preferable in terms of not causing such failures.
  • In the epitaxial substrate 10 including the buffer layer 5 configured in the above-described manner, due to the large compressive strain existing in the composition modulation layer 3 provided in the buffer layer 5, a state is achieved in which a tensile stress caused by a difference in the thermal expansion coefficient between silicon and the group-III nitride is suitably cancelled. Thereby, in the epitaxial substrate 10, a crack-free state is achieved and the amount of warping is suppressed to 100 μm or less.
  • The above-mentioned requirements that the value of n, which represents the number of laminations of the first composition layer 31 and the second composition layer 32, is about 40 to 100 and that the relationship of x(1)≧0.8 and x(n)≧0.2 is satisfied, are preferable in terms of providing a sufficient amount of compressive strain in the composition modulation layer 3 to thereby cancel the tensile stress caused by the difference in the thermal expansion coefficient.
  • That is, in the epitaxial substrate 10 according to this embodiment, the buffer layer 5 including the composition modulation layer 3 that serves as the strain-introduced layer is provided. This causes a large compressive strain to exist in the buffer layer 5, to suitably reduce a tensile stress caused in the epitaxial substrate 10 due to the difference in the thermal expansion coefficient between silicon and the group-III nitride. As a result, in the epitaxial substrate 10, a crack-free state is achieved and warping is reduced.
  • Since the buffer layer 5 is formed on the second base layer 2 b in which an accumulation of strain energy is suppressed as described above, the effect of canceling the tensile stress is not hindered by any strain energy accumulated in the second base layer 2 b.
  • Moreover, repeatedly laminating the first composition layer 31 and the second composition layer 32 increases the total film thickness of the epitaxial film itself. In general, in a case where a HEMT device is prepared using the epitaxial substrate 10, as the total film thickness thereof increases, the breakdown voltage of the HEMT device becomes higher. Thus, the configuration of the epitaxial substrate 10 according to this embodiment also contributes to increase of the breakdown voltage.
  • <Increase of Breakdown Voltage of Epitaxial Substrate>
  • The epitaxial substrate 10 according to this embodiment is also characterized by high breakdown voltage properties because of providing of the buffer layer 5 (and more specifically the composition modulation layer 3) having the above-described configuration.
  • In the epitaxial substrate 10 in which the composition modulation layer 3 is formed so as to satisfy the relationship of x(1)≧0.8 and x(n)≦0.2 and in which the total film thickness of the entire epitaxial film except the base substrate 1 is 4.0 μm or less, a high breakdown voltage of 600V or more is achieved. In this epitaxial substrate 10, crack-free is achieved and the amount of warping is reduced to about 60 μm to 70 μm. In this embodiment, the breakdown voltage means a voltage value at which a leakage current of 1 mA/cm2 occurs in a case where the voltage is applied to the epitaxial substrate 10 while being increased from 0V.
  • If the number of repetitions of lamination of the composition modulation layers 3, the total film thickness of the entire epitaxial film, and the total film thickness of the second composition layers 32 are appropriately set, the epitaxial substrate 10 having a higher breakdown voltage can be obtained. For example, an epitaxial substrate in which the total film thickness of the entire epitaxial film is 5 μm and the breakdown voltage is 1000V or higher, and an epitaxial substrate in which the total film thickness of the entire epitaxial film is 7 μm and the breakdown voltage is 1400V or higher, can be achieved.
  • As described above, in this embodiment, the buffer layer including the composition modulation layer is provided between the base substrate and the function layer, the composition modulation layer being formed by the first composition layer and the second composition layer being alternately laminated in such a manner that the Al mole fraction in the second composition layer decreases in an upper portion. Accordingly, a crack-free epitaxial substrate having an excellent crystal quality and excellent breakdown voltage properties can be obtained in which a silicon substrate, which is easily available in a large diameter at a low cost, is adopted as a base substrate thereof. In this epitaxial substrate, the amount of warping is suppressed to 100 μm or less.
    • Modification
  • In the epitaxial substrate 10, an interface layer (not shown) may be provided between the base substrate 1 and the first base layer 2 a. In one preferable example, the interface layer has a thickness of about several nm and is made of amorphous SiAluOvNw.
  • In a case where an interface layer is provided between the base substrate 1 and the first base layer 2 a, a lattice misfit between the base substrate 1 and the second base layer 2 b, and the like, is more effectively relieved, and the crystal quality of each layer formed thereon is further improved. That is, in a case where an interface layer is provided, an AlN layer that is the first base layer 2 a is formed such that the AlN layer has a concavo-convex shape similar to a case where no interface layer is provided and such that the amount of crystal grain boundaries existing therein is reduced as compared with the case where no interface layer is provided. Particularly, the first base layer 2 a having improvement in the half width value of the (0002) X-ray rocking curve is obtained. This is because, in a case where the first base layer 2 a is formed on the interface layer, nucleus formation of AlN, which will make the first base layer 2 a, is less likely to progress than in a case where the first base layer 2 a is formed directly on the base substrate 1, and consequently the growth in the horizontal direction is promoted as compared with when no interface layer is provided. The film thickness of the interface layer is to an extent not exceeding 5 nm. In a case where such an interface layer is provided, the first base layer 2 a can be formed such that the half width of the (0002) X-ray rocking curve is in a range of 0.5 degrees or more and 0.8 degrees or less. In this case, the function layer 6 can be formed with a more excellent crystal quality in which the half width of the (0002) X-ray rocking curve is 800 sec or less and the screw dislocation density is 1×109/cm2 or less.
  • The formation of the interface layer is achieved by, after the silicon wafer reaches the first base layer formation temperature and before the first base layer 2 a is formed, introducing only an TMA bubbling gas into the reactor to expose the wafer to an TMA bubbling gas atmosphere.
  • Furthermore, in the formation of the first base layer 2 a, at least one of Si atoms and O atoms may diffuse and form a solid solution in the first base layer 2 a, or at least one of N atoms and O atoms may diffuse and form a solid solution in the base substrate 1.
    • EXAMPLES
  • As an example, a plurality of types of epitaxial substrates 10 were prepared, which were different from one another in terms of the layer configuration of the buffer layer 5. Table 1 shows a basic configuration of the epitaxial substrates 10 according to the example, and more specifically, materials for forming the respective layers and the film thicknesses of the respective layers.
  • TABLE 1
    Name Material Film Thickness
    Function Layer Barrier Layer Al0.2Ga0.8N  25 nm
    Channel Layer GaN 700 nm
    Termination Layer AlN A nm
    Composition Second AlxGa1−xN B nm (A + B) × n
    Modulation Composition nm
    Layer Layer
    First AlN A nm
    Composition
    Layer
    Second Base Layer/First Al0.1Ga0.9N/AlN 140 nm
    Base Layer
    Base Substrate Si (111) 525 nm
  • As shown in Table 1, in this example, the materials and the film thicknesses of the base substrate 1, the base layer 2 (the first base layer 2 a and the second base layer 2 b), and the function layer 6 were the same for all the epitaxial substrates 10. The function layer 6 was configured as two layers of the channel layer and the barrier layer.
  • On the other hand, both the first composition layer 31 and the termination layer 4 were made of AlN, but their film thickness was different among specimens. In Table 1, this is indicated by the variable A (nm). Likewise, the film thickness of the second composition layer 32 is indicated by the variable B (inn). Here, n represents the number of each of the first composition layers 31 and the second composition layers 32.
  • In this example, the values of A, B, and n, and the compositional grading were variously changed. Thereby, 14 types of epitaxial substrates 10 (specimens No. 1 to No. 14) in total were prepared.
  • As a comparative example, all the n second composition layers 32 were given the same Al mole fraction, and thereby eight types of epitaxial substrates 10 (specimens No. 15 to No. 22) in which no compositional grading was given to the second composition layers 32 were prepared. In the comparative example, the same preparation conditions as those of the example were adopted, except for the second composition layer 32.
  • Table 2 shows, with respect to each specimen, the values of A, B, and n, the value of the Al mole fraction x(i) in the i-th one of the second composition layers 32 as counted from the base substrate 1 side, the total thickness of the composition modulation layer 3, and the total thickness of the epitaxial film.
  • TABLE 2
    Total Thickness Total
    of Composition Thickness of
    Specimen A B Modulation Layer Epitaxial Film
    No. (nm) (nm) n x(i) (nm) (nm)
    Example 1 5 15 100 1 − (i/n) 2000 2870
    2 5 20 80 2000 2870
    3 5 25 70 2100 2970
    4 5 35 50 2000 2870
    5 7.5 15 90 2025 2897.5
    6 7.5 25 60 1950 2822.5
    7 10 25 60 2100 2975
    8 10 35 45 2025 2900
    9 5 15 100 1 − 0.012 × i (i = 1 to 50) 2000 2870
    0.8 − 0.008 × i (i = 51 to 100)
    10 5 15 100 1 − 0.008 × i (i = 1 to 50) 2000 2870
    1.2 − 0.012 × i (i = 51 to 100)
    11 5 15 100 1 − 0.016 × i (i = 1 to 25) 2000 2870
    0.7 − 0.004 × i (i = 26 to 75)
    1.6 − 0.016 × i (i = 76 to 100)
    12 5 15 100 1 − 0.004 × i (i = 1 to 25) 2000 2870
    1.3 − 0.016 × i (i = 26 to 75)
    0.4 − 0.004 × i (i = 76 to 100)
    13 5 15 100 0.8 (i = 1 to 25) 2000 2870
    0.6 (i = 26 to 50)
    0.4 (i = 51 to 75)
    0.2 (i = 76 to 100)
    14 5 20 90 0.9 (i = 1 to 10) 2250 3120
    0.8 (i = 11 to 20)
    0.7 (i = 21 to 30)
    0.6 (i = 31 to 40)
    0.5 (i = 41 to 50)
    0.4 (i = 51 to 60)
    0.3 (i = 61 to 70)
    0.2 (i = 71 to 80)
    0.1 (i = 81 to 90)
    Comparative 15 5 15 100 0 2000 2870
    Example 16 5 20 80 0 2000 2870
    17 5 25 70 0 2100 2970
    18 5 35 50 0 2000 2870
    19 5 15 100 0.1 2000 2870
    20 5 15 100 0.2 2000 2870
    21 5 15 100 0.3 2000 2870
    22 5 15 100 0.4 2000 2870
  • A specific process for preparing each of the epitaxial substrates 10 is as follows.
  • Firstly, until the formation of the second base layer 2 b, the same procedure was performed for any of the specimens. A (111) plane single crystal silicon wafer (hereinafter, a silicon wafer) of four inches having the p-type conductivity and having a substrate thickness of 525 μm was prepared as the base substrate 1. The prepared silicon wafer was subjected to dilute hydrofluoric acid cleaning using dilute hydrofluoric acid having a composition of hydrofluoric-acid/pure-water=1/10 (volume ratio), and subjected to SPM cleaning using cleaning liquid having a composition of sulfuric-acid/aqueous-hydrogen-peroxide=1/1 (volume ratio). Thus, a state was created in which an oxide film having a thickness of several Å was formed on the wafer surface, which was then set in a reactor of a MOCVD apparatus. Then, a hydrogen/nitrogen mixed atmosphere was created in the reactor, and the pressure in the reactor was set to be 15 kPa. Heating was performed until the substrate temperature reached 1100° C. that is the first base layer formation temperature.
  • When the substrate temperature reached 1100° C., a NH3 gas was introduced into the reactor, and the substrate surface was exposed to a NH3 gas atmosphere for one minute.
  • Then, a TMA bubbling gas was introduced into the reactor with a predetermined flow ratio, to react NH3 with TMA, so that the first base layer 2 a whose surface has a three-dimensional concavo-convex shape was formed. At this time, the growing speed (film formation speed) of the first base layer 2 a was set to be 20 nm/min, and the target average film thickness of the first base layer 2 a was set to be 100 nm.
  • After the first base layer 2 a was formed, then the substrate temperature was set to be 1100° C. and the pressure in the reactor was set to be 15 kPa. A TMG bubbling gas was further introduced into the reactor, to react NH3 with TMA and TMG, so that an Al0.1Ga0.9N layer serving as the second base layer 2 b was formed so as to have an average film thickness of about 40 nm.
  • Subsequent to the formation of the second base layer 2 b, the buffer layer 5, and more specifically, the composition modulation layer 3 and the termination layer 4, were prepared in accordance with the values of A, B, n, and x(i) shown in Table 2.
  • The following is an outline of specific set values for A, B, and n in the example and the comparative example.
  • A: example (5 nm, 7.5 nm, 10 nm), comparative example (5 nm);
  • B: example (15 nm, 20 nm, 25 nm, 35 nm), comparative example (15 nm, 20 nm, 25 nm, 35 nm); and
  • n: example (45, 50, 60, 70, 80, 90, 100), comparative example (50, 70, 80, 100).
  • In the formation of the buffer layer 5, the substrate temperature was set to be 1100° C., and the pressure in the reactor was set to be 15 kPa. The same material gas as for the formation of the base layer 2 was used.
  • In the specimens according to the example, the compositional grading given to the second composition layer 32, that is, the Al mole fraction in each second composition layer 32<i> among the second composition layers 32<1> to 32<n>, was broadly classified into the following three manners. FIG. 3 is a diagram illustrating how the Al mole fraction was changed in main specimens. It is to be noted that any specimen was formed so as to satisfy the relationship of x(1)≧0.8 and x(n)≦0.2.
  • Nos. 1 to 8: the Al mole fraction x(i) was monotonically decreased at a constant rate;
  • Nos. 9 to 12: the Al mole fraction x(i) was monotonically decreased but the rate of change in the course of the decrease was varied; and
  • Nos. 13 to 14: the Al mole fraction x(i) was changed stepwise.
  • On the other hand, in the specimens according to the comparative example, the value of the Al mole fraction x in the second composition layer 32 was set to be any of 0, 0.1, 0.2, 0.3, and 0.4.
  • For any of the specimens according to the example and the comparative example, after the buffer layer 5 was formed, the channel layer made of GaN and serving as the function layer 6 was formed with a thickness of 700 nm, and then the barrier layer made of Al0.2Ga0.8N was further formed with a thickness of 25 nm. In the formation of the function layer 6, the substrate temperature was set to be 1100° C., and the pressure in the reactor was set to be 15 kPa. The same material gas as for the formation of the base layer 2 was used.
  • Through the above-described process, 22 types of epitaxial substrates 10 were obtained in total.
  • For the obtained epitaxial substrates 10, the presence or absence of occurrence of cracking was visually checked. Additionally, the amount of warping was measured using a laser displacement gauge. Here, for the epitaxial substrates 10 where cracking occurred, the breakdown voltage was measured in a region not including the cracking. Results of the measurements are shown in Table 3.
  • TABLE 3
    Specimen Occurrence of Warping Breakdown
    No. Cracking (μm) Voltage (V)
    Example 1 Not Observed 65 750
    2 Not Observed 62 800
    3 Not Observed 59 875
    4 Not Observed 61 875
    5 Not Observed 65 675
    6 Not Observed 62 750
    7 Not Observed 62 750
    8 Not Observed 64 800
    9 Not Observed 62 750
    10 Not Observed 63 750
    11 Not Observed 64 750
    12 Not Observed 62 750
    13 Not Observed 63 750
    14 Not Observed 68 850
    Comparative 15 Occurred at 20 mm 135 120
    Example from Outer
    Periphery
    16 Occurred at 20 mm 142 145
    from Outer
    Periphery
    17 Occurred at 20 mm 156 180
    from Outer
    Periphery
    18 Occurred at 20 mm 156 160
    from Outer
    Periphery
    19 Occurred at 20 mm 162 320
    from Outer
    Periphery
    20 Occurred at 20 mm 163 420
    from Outer
    Periphery
    21 Occurred at 20 mm 169 510
    from Outer
    Periphery
    22 Occurred at 20 mm 171 590
    from Outer
    Periphery
  • As shown in Table 3, in all the specimens according to the comparative example, cracking occurred at 20 mm from the outer periphery. On the other hand, in the specimens according to the example, no cracking was observed irrespective of how the compositional grading was given to the second composition layer 32.
  • In the specimens according to the comparative example where cracking occurred, the amount of warping was at least 135 μm, which largely exceeds 100 μm, while in the specimens according to the example where no cracking occurred, the amount of warping was suppressed to about 60 μm to 70 μm.
  • The above-mentioned results indicate that forming the composition modulation layer 3 by alternately laminating the first composition layer 31 and the second composition layer 32 in such a manner that the compositional grading is given to the second composition layer 32 as described in the example, is effective in achieving a crack-free state of the epitaxial substrate 10 and suppression of warping therein.
  • In the specimens according to the comparative example, the second composition layer has a relatively small thickness, and therefore it would be guessed that the second composition layer itself grew in a coherent state. Despite this, cracking occurred in the comparative example. Accordingly, it is considered that, in a case where, as in the comparative example, the first composition layer and the second composition layer are merely alternately laminated without any compositional grading given to the second composition layer, the compressive strain is introduced into each individual second composition layer 32 but the total sum thereof is not sufficient for canceling the tensile stress.
  • As for the breakdown voltage, in the specimens according to the comparative example, even the highest breakdown voltage was below 600V, whereas in all the specimens according to the example, the breakdown voltage was 600V or higher. These results indicate that forming the composition modulation layer 3 so as to satisfy at least the relationship of x(1)≧0.8 and x(n)≦0.2 can provide the epitaxial substrate 10 having a high breakdown voltage.

Claims (5)

1. An epitaxial substrate in which a group of group-III nitride layers are formed on a base substrate made of (111)-oriented single crystal silicon such that a (0001) crystal plane of said group of group-III nitride layers is substantially in parallel with a substrate surface of said base substrate, said epitaxial substrate comprising:
a buffer layer including a composition modulation layer that is formed of a first composition layer made of AlN and a second composition layer made of a group-III nitride having a composition of AlxGa1-xN (0≦x<1) being alternately laminated; and
a crystal layer formed on said buffer layer,
wherein
said composition modulation layer is formed so as to satisfy the relationship of

x(1)≧x(2)≧ . . . ≧x(n−1)≧x(n); and

x(1)>x(n),
where n represents the number of laminations of each of said first composition layer and said second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of said second composition layers as counted from said base substrate side, to thereby cause a compressive strain to exist in said composition modulation layer such that said compressive strain increases in a portion more distant from said base substrate.
2. The epitaxial substrate according to claim 1, wherein
each of said second composition layers is formed so as to be in a coherent state relative to said first composition layer.
3. The epitaxial substrate according to claim 1, further comprising:
a first base layer made of AlN and formed on said base substrate; and
a second base layer made of AlpGa1-pN (0≦p<1) and formed on said first base layer,
wherein
said first base layer is a layer with many crystal defects configured of at least one kind from a columnar or granular crystal or domain,
an interface between said first base layer and said second base layer defines a three-dimensional concavo-convex surface,
said buffer layer is formed immediately on said second base layer.
4. A method for manufacturing an epitaxial substrate for use in a semiconductor device, said epitaxial substrate having a group of group-III nitride layers formed on a base substrate made of (111)-oriented single crystal silicon such that a (0001) crystal plane of said group of group-III nitride layers is substantially in parallel with a substrate surface of said base substrate, said method comprising:
a buffer layer formation step for forming a buffer layer; and
a crystal layer formation step for forming a crystal layer above said buffer layer, said crystal layer being made of a group-III nitride,
wherein
said buffer layer formation step includes a composition modulation layer formation step for forming a composition modulation layer by alternately laminating a first composition layer made of AlN and a second composition layer made of a group-III nitride having a composition of AlxGa1-xN (0≦x<1),
in said composition modulation layer formation step, said composition modulation layer is formed in such a manner that:
the relationship of:

x(1)≧x(2)≧ . . . ≧(n−1)≧x(n); and

x(1)>x(n),
is satisfied, where n represents the number of laminations of each of said first composition layer and said second composition layer (n is a natural number equal to or greater than two), and x(i) represents the value of x in i-th one of said second composition layers as counted from said base substrate side; and
each of said second composition layers is in a coherent state relative to said first composition layer.
5. The method for manufacturing the epitaxial substrate according to claim 4, further comprising:
a first base layer formation step for forming a first base layer on said base substrate, said first base layer being made of AlN; and
a second base layer formation step for forming a second base layer on said first base layer, said second base layer being made of AlpGa1-pN (0≦p<1),
wherein
in said first base layer formation step, said first base layer is formed as a layer with many crystal defects configured of at least one kind from a columnar or granular crystal or domain, such that a surface thereof is a three-dimensional concavo-convex surface,
in said composition modulation layer formation step, said composition modulation layer is formed immediately on said second base layer.
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